WO1980002143A1 - Process for preparing gel-like composition of acetylene high polymer,and process for fabrication thereof - Google Patents

Process for preparing gel-like composition of acetylene high polymer,and process for fabrication thereof Download PDF

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Publication number
WO1980002143A1
WO1980002143A1 PCT/JP1980/000053 JP8000053W WO8002143A1 WO 1980002143 A1 WO1980002143 A1 WO 1980002143A1 JP 8000053 W JP8000053 W JP 8000053W WO 8002143 A1 WO8002143 A1 WO 8002143A1
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Prior art keywords
acetylene
high polymer
gel
polymerization
solvent
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PCT/JP1980/000053
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English (en)
French (fr)
Japanese (ja)
Inventor
S Ikeda
Y Kobayashi
H Shirakawa
Original Assignee
Showa D
S Ikeda
Y Kobayashi
H Shirakawa
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Priority claimed from JP3628879A external-priority patent/JPS55128419A/ja
Priority claimed from JP3628379A external-priority patent/JPS55129404A/ja
Priority claimed from JP5024479A external-priority patent/JPS6028300B2/ja
Priority claimed from JP5401779A external-priority patent/JPS55145710A/ja
Priority claimed from JP5401879A external-priority patent/JPS55145711A/ja
Application filed by Showa D, S Ikeda, Y Kobayashi, H Shirakawa filed Critical Showa D
Priority to DE19803041421 priority Critical patent/DE3041421C2/de
Publication of WO1980002143A1 publication Critical patent/WO1980002143A1/ja

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/003—Thick film resistors
    • H01C7/005—Polymer thick films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F38/00—Homopolymers and copolymers of compounds having one or more carbon-to-carbon triple bonds
    • C08F38/02—Acetylene
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/125—Intrinsically conductive polymers comprising aliphatic main chains, e.g. polyactylenes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/141—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE
    • H10K85/143—Polyacetylene; Derivatives thereof
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to a method for producing a high-polymerized acetylene "gel composition of a book”! Or a porous acetylene high polymer, and a molding method. ⁇ Useful as a semiconductor.
  • Acetylene is polymerized using a so-called Ziegler's Natta catalyst, which is composed of a transition metal compound and an organic compound.
  • Ziegler's Natta catalyst which is composed of a transition metal compound and an organic compound.
  • the acetylene high polymer obtained in this way does not melt even when heated with a sword, and is easily degraded under heat, so it is molded by a molding method such as a normal thermoplastic resin. I can't.
  • no solution for dissolving the acetylene high-weight support has yet been found, and therefore, those who produce practically molded acetylene high polymers; S is limited to the following two methods .
  • _OMPI Polymerization is carried out on the surface coated with acetylene to form a film-like or fibrous acetylene polymer (Japanese Patent Publication No. 48-32581).
  • the transition metal compound " ⁇ " be used in an amount of more than 0.1 mol per 1 of the polymerization solvent.
  • a gel-like acetylene high polymer is also known to be obtained by polymerization using a special catalyst and hexane as a solvent.
  • the present inventors have found that in the above method (a), it is possible to obtain a solid molded article having mechanical strength.
  • the present invention provides (1) acetylene as (A) IVa, Ya,
  • Transition metal compounds containing at least one transition metal from ⁇ and V group transition metals and at least one of the [!], II 6, £ ⁇ and IV ⁇ group metals of the (5) table of contents In the polymerization using a metal compound containing a kind of metal, such as metal compound, a polymerization solvent containing 0.01 to 0.1 molno is included in the metal compound.
  • a forming sword characterized by producing a gel consisting of acetylene high-gravity ⁇ having a fibril structure and a polymerization solvent consisting of i9 and a polymerization solvent by performing polymerization in a gel.
  • the present invention also provides (2) a sword having a fibril structure in which a gel-like snout of an acetylene high polymer having a fibril structure having a solvent having a freezing point of ⁇ 50 to 50 C is freeze-dried.
  • the method of producing highly porous polyacetylene highly polymerized books is easy.
  • the present invention provides (3) an acetylene high polymer having a fibril structure 5 to
  • the gel sleeve obtained from (1) should be used as the gel sleeve formed from the high-polymerized 1 * -styrene having a fibril structure used in (2) and (3) of the present invention and the organic solvent. Needless to say, a gel other than the acetylene high polymer having a fibrinole structure and an organic solvent can be used except for (1).
  • Uniform gel-like shape that can be achieved by Manpo (1) of the present invention.
  • the shape can be made to have any shape and thickness by pressure molding as described in (3) above. It is extremely useful because the mechanical strength of the resulting molded article is extremely high.
  • the homogeneous gel-like polymerization catalyst (1) of the present invention is different from the special catalyst used in (c) above; Since the catalyst can be used, the cost of the catalyst can be significantly reduced; Furthermore, in the method (1) of the invention, a uniform gel can be formed, and since a powdery rose-like substance is not formed, a molded article formed by pressure molding is uniform and its mechanical change is sufficiently large.
  • the acetylene high-gravity porous material having a fibril structure which can be obtained by the method (2), can be of any desired bulk density depending on the polymerization conditions, and has excellent forming power.
  • Method or calendar processing method it is possible to easily make ⁇ or shape _ which can be easily formed into an arbitrary shape and an arbitrary thickness.
  • the porous acetylene high polymer is industrially very useful because it has a fibril structure and the resulting molded article has large mechanical changes.
  • the gel-like material referred to in the present invention is a gel-like material which is in a state of being swelled with a solvent in which fibrils of acetylene high polymer are entangled with each other. Is essentially different. BEST MODE FOR CARRYING OUT THE INVENTION
  • the transfer metal compound having at least one type of transition metal among the group IVa, Va, VIa, and VI transition metals used as the polymerization catalyst in the present invention is, specifically, titanium. emissions, vanadium, chromium, iron, cobalt, at the most a halogen atom or carbon atoms of the metal of the motor tungsten and motor Ribuden 2 0 ⁇ solid of completion alkyl group, an alkenyl group, Ariru (dr Z) group, Ryo aralkyl group A compound having a carboxylic acid residue, a phenoxide group, a carboxylic residue, a cyclopentagenenyl group, an acetylacetate residue, a carbon atom (carbonyl group), and a pyrididine; Complexes such as triphenylcarbine and dipyridyl are electron donating compounds.
  • transition metal compounds compounds of titanium, vanadin, iron, chromium, and cobalt are preferable, and compounds of titanium are particularly preferable.
  • transition formula metallization represented by the general formulas (I) to (! [] Can be used.
  • transition metal compounds include, but are not limited to, tetramethoxytitanium, tetraethoxytitanium, tetraw-propoxytitanium, tetrabutylpropoxytitanium, tetraw-butoxytitanium, Tetrisobutoxytitanium, Tetraoctadecyloxytitanium, Tetrafuenoxytitanium, Trisacetyl acetate Totitanium squirrel Ryo cetyl Ryo Setona Toku Russia-time, door squirrel ⁇ cetirizine Norre acetate Tonato cobalt, titanium O carboxymethyl Ryo cetyl Ryose Tonato, is vanadium O carboxymethyl Ryo Sechiruase Tonato like there ⁇ 0
  • the organometallic compound used in the present invention is a metal compound having at least one metal among the metals belonging to groups 11a, Ib, I ⁇ and IV of the periodic table.
  • M is a metal belonging to the group I1A, fl, or IV with a period of ⁇ , or at most 20 alkyl groups or alkenyl having at most 20 carbon atoms.
  • J which may be single or heterogeneous, at least one of which is a hydrogen atom or the valence group, and n is the highest valence number of the metal or less. Is a number)
  • metal ties used in the present invention typical ones are magnesium, calcium, and sub! &, Boron, Aluminum, Carbide, Silicon and Tin Metallic Compounds + + Of course] 3, especially Magnesium, Zinc, Aluminum and Tin: Metallization is preferred, and Aluminum-based compounds are preferred.
  • the existing compounds are: triethyl aluminum, tri-impregnated aluminum, tri-hexyl, aluminum, jetinole, norm, etc.
  • the amount of anti-reaction between the aluminum and the water is lower than the ratio of the petroleum to the aluminum oxide and the triethyl aluminum and the water. The ratio is 1: 0.5 (molar ratio).
  • Can be Other finished aluminum compounds include aluminum
  • the killing formula used in the present invention as the organometallic compound is as follows.
  • K z and ⁇ 3 may be j- or different, and are a halogen atom or an alkyl group or an alkoxy group having at most 10 carbon atoms.
  • 5 is a halogen atom or an alkyl or alkoxy group having at most 10 carbon atoms or a general formula.
  • One of the aluminum siloxane siloxes used in the present invention is trimethyldimethyl-siloxalene, tri Methynorethetinole-siloxalen, tri-methyltinol-n-propynole-siloxalen, trimethinole-diisobutyl-siloxalen, trimethyltinol-siloxalen, trichloride methylinol-siloxalen, dimethinoletinol -Siloxalene, trimethoxydimethinole-Siloxalen ⁇ Trietinoresimetinole-Siloxalene, Trimethinoresinethoxy-Siloxalen, Trimethyldimethoxy-Siloxalen and Trimethoxyd
  • an organic metal compound is used.
  • i 1 , R 2 and i may be single or different, Z element or an alkyl group having at most 10! Carbon atoms, and R 4 is often a halogen atom or carbon atom. (Although these are also 10 alkyl groups.)
  • typical ones are getyl aluminum dimethyl imide, and getyl aluminum dimethyl imide. ⁇ , ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w
  • the kill formula of the dialxane compound used as a gold halide is represented by the following formula.
  • dialumoxane compounds used in the present ⁇ a include tetramethyldialumoxane, tetramethyldilumoxane, rumolexan, tetraisobutinoresin-noremoxane, -dimethyl-3, 3 Jetyldilumoxane, tetraisobutyldilumoxane, 1,1-dimethyl-3,3-diimptyldialumoxane, tetradecyldialmoxane, trimethyldialumoxane chloride and triethyldialumoxane can give.
  • t ⁇ of the organometallic compounds other than the organic aluminum compound and the tenth compound include getyl magnesium, chloridylethyl magnesium, hydridylmethylmagnesium chloride, and the like.
  • a ⁇ l yl Magnesium: normal propyl magnesium chloride, tertiary-butylmagnesium lip, odor 1 phenyl magnesium, dipheninole
  • examples of the compound used in the present invention include double salts of the above-mentioned organic compounds (for example, lithium aluminum tetrahydride and calcium tetraethyl).
  • these organometallic compounds may be used alone or in combination of two or more.
  • the ratio of the metal compound to the transition metal of the metal compound is in the range of 1 to 100% by mole, preferably 1 to 50, particularly preferably 1 to 2 5
  • the transition metal compound and the metallization can be used in combination with the third component, if necessary, to control the polymer yield, polymerization rate, and the like.
  • the third component includes an impurity compound such as alcohol, peroxide, and calcium.
  • OMPI Bonn ⁇ anhydride, acid chloride, 'ester, ketone, etc. can be mentioned as examples.
  • Other compounds containing nitrogen, compounds containing sulfur, compounds containing halogen, molecular iodine, etc. Lewis or the like can also be used.
  • any organic solvent can be used as long as it is inert to the catalyst and is liquid for polymerization.
  • the concentrated fatigue of the ⁇ -gold compound in the catalyst system depends on the catalyst used and the polymerization conditions. 0.001 to 0.1 mole, preferably 0.001 to 0.1 mole, more preferably 0.01 to 0.1 mole of car Eg with respect to 1 It is necessary to carry out the polymerization of the polymer. If the amount of the transition metal exceeds 0.1 mol per 1 ⁇ of the polymerization solution, it is difficult to process the resulting gel.
  • the contact solution may be uniform or non-uniform, but from the viewpoint of easy removal of the catalyst, the contact solution and the solution are preferably uniform.
  • the polymerization temperature is not particularly limited, but is usually preferably from 100 to 300 ° C, and from the viewpoint of easy handling, it is particularly preferably from 180 to 200 ° C.
  • the degree of contact between the transition metal compound and the metal compound and the aging conditions of the catalyst system cannot be specified unconditionally because they are determined by the amount and weight of the catalyst component used. In the 0 ⁇ 100C car ⁇ range] ?, if necessary, it is possible to ripen the acetylene before starting, and the ⁇ is usually 1 20 ⁇ : L0C car ⁇ 3 ⁇ 41 It is.
  • Transition metal compound ⁇ Of course, the sword for the direct dissolution of metallic compounds and acetylene gas ⁇ )
  • the trace is not particularly limited, but for example,
  • the polymerization can be performed in a state where the polymerization solution is kept still, or in a state where the polymerization solution is mechanically stirred.
  • the polymerization temperature g the catalyst system: ⁇
  • the catalyst system it is possible to control the steric structure of the high-molecular-weight polymer, it is generally possible to produce a flexible poly (ethylene glycol) polymer having a low cis content and a high cis-content when the polymerization temperature is low.
  • a high content acetylene high polymer is produced.
  • the pressure of the acetylene gas in the polymerization is not particularly limited, but practically, it is preferable to perform the pressure at 10 atm or less.
  • the polymerization can be performed by a method of supplying acetylene gas to the surface of the polymerization solution, or by a method of directly introducing acetylene gas into the polymerization solution.
  • a method for removing ⁇ ⁇ ⁇ ⁇ from the acetylene high polymerization I-gel obtained by the polymerization the usual removal method, for example, washing with a solvent that dissolves the catalyst i3 ⁇ 4 # is used, In particular, it can be used without removing the catalyst.
  • the uniform gel of the acetylene-highly polymerized book thus obtained can be easily formed into a uniform molded article having a large mechanical strength having an arbitrary shape and a desired thickness by performing a sword pressure molding.
  • the high-acetylene polymer thus obtained has a fibril structure.
  • the acetylene high polymer having a fibrous structure having a fibrous structure referred to in the present invention is a crystalline form of disordered microcrystalline having a diameter of 200 to 60 OA. It is a high polymer, and it is a linear acetylene high polymer consisting of cis or trans conjugated double bonds. .
  • the freezing point is 15 .
  • ⁇ ⁇ * and a 1 volume: f are gelled in the form of “ ⁇ ”, those produced by any method can be used again.
  • Specific examples of the production method include the method of the present invention.
  • the acetylene high polymer may have any cis-transition ratio, and the solvent in the gel-like material may be any one. However, at least during freeze-drying, the freezing point must be from ⁇ close to the chamber.
  • bearing medium refers to a carrier medium of * E having a freezing point of 1 to 50 ° C., preferably —31: to 20 ° C. Any solvent having a freezing point outside the above range can be used, but it is industrially disadvantageous because the equipment for freeze-drying is expensive.
  • the amount of the above-mentioned solvent in the gel is from 1 to 100 parts by weight per 1 part by weight of the acetylene high polymer. It is difficult to obtain a high porous acetylene high polymer. Freeze-drying may be performed by a method commonly used in the art, for example, sublimation of the lysate frozen in a vacuum device *. The temperature for freezing and drying depends on the solvent used, but is usually in the range of 150 to 50 ° C.
  • the acetylene high polymer in the ⁇ gel state can be arbitrarily adjusted by adjusting the polymerization conditions. ⁇ Since the bulk density of the porous acetylene high polymer can be adjusted ⁇ 0.1? No! ⁇ 0 0 0 0 1? It can be adjusted to the range of no.
  • the porous acetylene high polymer obtained by the production method of the present invention may be used as it is, or may be molded! It may be used as a product.
  • the gel of the present invention comprising 5 to 95% by weight of a heavy-weight acetylene body having a fibril structure and 95 to 5% by weight of inactive 'raw-dissolved' is subjected to pressure 1. Pressurizing at more than 0 ° C ⁇
  • a special method of molding acetylene high polymer; the gel-like material used in the past consists of fibril resin, which is composed of acetylene high gravity ⁇ : As long as it is a gel, it can be made by any method! You can use it.
  • a specific example is the Manpo method of the present invention, but is not necessarily limited to this.
  • OMPI IPO Absent OMPI IPO Absent.
  • the cis-trans of acetylene high-gravity ⁇ can use any 3 ⁇ 4.
  • Solvents used in the present invention are particularly marketable, but typical solvents include aliphatic or aromatic hydrocarbons, halogenated hydrocarbons, ethers, carboxylic esters, and the like. ⁇ No 7J items, ketones, etc. can be opened.
  • Typical examples are benzene, toluene, gicillen, etilbenzen methinolefeninole, ethinolef enoinole, terinolef enoinole, and tertiary dipheninole.
  • a polar solvent such as an aliphatic or aromatic alcohol, carboxylic acid, etc. May be directly lysed.
  • the amount of the acetylene resin used in the gel form used in the present invention is 5 to 95% by weight.o If the acetylene high direct bond in the gel form is less than 5 fold, the wall thickness is uniform. Is it difficult to manufacture molded products? If the weight of the acetylene in the gel is more than 95 M, it is difficult to form a molded article of any shape by pressure molding.
  • ⁇ of the pressure-molded ⁇ is not more than 100 C, preferably not more than 80 C, and if it exceeds 100 t :, the acetylene high polymer becomes unsuitable due to deterioration of the acetylene high polymer. is there.
  • Pressure molding at a low pressure is preferred because the acetylene-rich s coalescence tends to deteriorate, but molding at 150 ° C. or less is not practical.
  • the pressure of the molding 'if is more than 1 ⁇ , preferably 5 Z c ⁇
  • a molded article having a sufficiently large ⁇ ] ⁇ J strength ⁇ can be obtained.
  • the residual-dissolved ⁇ can be used as it is in practical use-it is acceptable. It may be easily removed, but it may be removed by a method such as vacuum drying.
  • a molded product having a high mechanical strength and a predetermined shape and thickness can be easily obtained.
  • the electrical resistance of the molded article of the acetylene high polymer obtained in this manner is extremely low, and shows various characteristics peculiar to semiconductors.
  • the air conductivity can be increased from 10 to 10 3 ⁇ - 1 'cm. - it can be freely controlled to Rukoto over a wide range of 1.
  • electron-accepting compounds are iodine, iodine, bromine iodide, arsenic pentafluoride, antimony pentafluoride, silicon tetrafluoride, phosphorus pentafluoride, phosphorus pentafluoride, Lumichloride, Lumibromide, Peroxydisulfuryl difluoride, Sulfur ⁇ , Shixiao ⁇ , Full-sulfur ⁇ sulfur ⁇ , Triflusulfur-lumetansulfon, Black sulfur ⁇ , Boron trichloride, Trisulfur Boron bromide, zirconium trioxide, oxygen dioxide, etc. can be opened.
  • Representative examples of the electron donating compound include sodium, potassium, and cesium.
  • Toluene 200 which was ovalized according to the usual method as heavy and dissolved, was added to the glassy reaction of 1, which was completely straightened with nitrogen gas, and tetrabutyl iron was used as a catalyst. 7.34 millimoles were sequentially charged in the chamber ⁇ to prepare a catalyst solution, and the catalyst solution was a homogeneous solution. The reactor was cooled at night with nitrogen and the nitrogen gas in the yarn was evacuated with a vacuum pump.
  • the gel-like acetylene polymer that has been severely moistened in toluene is a homogenous substance in which cut-off microcrystals (fibrils) having a diameter of 200 to 500 A are entangled with the non-woven fibers lj. Rose-shaped polymer is generated and
  • This film was a P-type semiconductor with an “air conduction” (DC fi terminal method) of 2 and 5.3 ⁇ 10 ⁇ — 1 'cm _ 1 .
  • the S vessel was cooled with liquid oxygen, and the nitrogen gas in the system was evacuated with a vacuum pump.
  • the reactor was then turned into the chamber ⁇ , and the magnetic stirrer was used to remove the solvent ⁇ volume 3 ⁇ 4 : 1) Atmospheric pressure of acetylene gas was blown in.7) 10 minutes after the polymerization reaction was started, the system ⁇ : became an agar-like gel-like material. ⁇ 3 ⁇ 4 ⁇ ⁇ The whole system was black-brown agar-like.
  • the unreacted acetylene gas was gradually removed, and the mixture was washed four times with ⁇ combined ⁇ 200 of 1: 1 (volume, ratio) of methanol and toluene. .
  • the resulting gel-like " ⁇ is a real Jg i7 [j 1 and a uniform 3 ⁇ 4 gel-like material] 3. There was a film.
  • OMPI Tris-acetyl-cetonato iron 5.0 millimol and triisoptyl-luminium 1 were used instead of tritium-butoxytitanium and triethyl-luminum used in Example 1. . 5 0 except for using the Mi Rimoru is carried Kiyoshi 1 exactly I hundred] like the preparation preliminary acetylene catalytic polymerization 3 ⁇ 4 line 3 ⁇ 4 Ii example 1 and I Tsukasa like 3 ⁇ 4 -. gel 3 ⁇ 4 ⁇ T ⁇ o
  • a glass reaction vessel (1) completely replaced with nitrogen gas, toluene (200) purified according to a conventional method as a polymerization solvent, tetrabutoxytitanium (0.01 mmol) and triethylamine (0.1 mol) as catalysts were used.
  • the reaction solution was charged at room temperature to prepare a catalyst solution.
  • the catalyst solution was 1 volume in average.
  • the reactor was cooled with sputum humor and the humid gas in the system was evacuated with a vacuum pump.
  • This powdery acetylene high polymer was washed four times with purified toluene 200 times, washed and dried in vacuo to obtain a powdery acetylene high polymer.
  • This powdery acetylene high polymer was sandwiched between ⁇ and ⁇ -plates, and pressed at room temperature under a pressure of 100 0 / C ⁇ . It was not in film form.
  • Glass 1 completely replaced with nitrogen gas ⁇ Into a container, 200 ⁇ m of toluene, purified by a conventional method, as a polymerization solvent, and 40 ⁇ mol of tetrabutoxytitanium and 80 ⁇ mol of triethylaluminum as catalysts. A catalyst solution was prepared by sequentially charging. The catalyst; volume was a homogeneous solution.
  • Example 1 and I After Example 1 and I, and then pressure-molded as in Example 1, a uniform film was not obtained.
  • Example 1 While carrying out the polymerization of acetylene,
  • the film was removed in the same manner as in Example 1. Then, the film-like gel was pressed and pressed at a pressure of 1 ton between the foamed ⁇ -plates to increase the metallic luster. A film of acetylene high polymer with high mechanical strength was found.
  • OMPI Remove the rengas and repeat the system four times with a 200 elliptical curve while keeping the intensity at 1 78 C! ) Return washing. Dissolved after cooling; dark brown at night, catalyst completely removed.
  • the gel-like acetylene polymer swelled in toluene is a gel-like material in which fibrils with a diameter of 300 to 500 A are irregularly intertwined! ), No powdery or bulky polymer was formed.
  • the gel-like phlegm plate was press-molded at room temperature at 100 K ° C. When pressed, it had a reddish-brown metallic luster and large mechanical strength.
  • the film was r r.
  • the Fi Lum electrical conductivity 9. (a DC four-terminal method) 2 0 C 4 X 1 0 one 7 n - 1 - cm - 1 of? ) Type semiconductor.
  • Example 8 In Example 7, except that ⁇ -heptane was used in place of toluene used as the polymerization solvent, the procedure was completely the same as in Example 7, except that ⁇ -heptane was used.
  • the polymerization of acetylene was carried out according to the method of Mr. I. -The obtained gel was press-molded by the same method as that of ⁇ !
  • the acetylene was dissolved by a mild amount in 5. Then, a catalyst solution was prepared by adding 1.50 millimoles of triisobutyl chloride. The catalyst solution was a homogeneous solution.
  • the ⁇ of the 5-5 units was brought to room temperature, and purified acetylene gas at a pressure of 1 atm was injected. 10 minutes after the start of the polymerization reaction, the entire system 1 * is a gel-like agar
  • Example 7 In the same manner as in Example 7, the catalyst was adjusted in the same manner as in Example 7: ⁇ and acetylene, and the actual gel was similar to W ⁇ 7.
  • Example 9 In place of the tetrabutoxytitanium and trisobutinolealuminum used in Example 9, the amount of tris-butyltinacetone was reduced to 0.5 mmol and triseptylaluminum. Except that millimol was used, the medium was cleaved and acetylene was polymerized in the same manner as in Example 9 to obtain a gel-like material similar to that in Example 9.
  • Toluene which was ovalized according to a conventional method, was charged into a glass reaction vessel (1), which was completely exchanged with nitrogen gas, according to a conventional method, and cooled to —78 C. After removing the elemental sulfur gas in the system with, the acetylene gas is blown in at 1 atm to dissolve the acetylene by the saturated amount, and then the catalyst is tetrabutyloxytitanium 0.01 mimol and triethyl. preparing a catalyst solution Ruminiu ⁇ 0.1 to 1 Mi Rimoru sequentially one 7 8 C ⁇ 3 ⁇ 4 Nde
  • OMPI WIPO did.
  • the catalyst solution was homogeneous.
  • the reactor was cooled with liquid nitrogen and the nitrogen gas in the system was evacuated with a vacuum bomb.
  • This powdery acetylene high-coagulated product was washed four times with purified water: ⁇ toluene 200, and then dried to obtain a powdery acetylene high polymer.
  • the weight of acetylene was completely determined in the same manner as in Example 7. As a result, some of the acetylene-rich polymer was gel-like, but most of the acetylene-rich polymer was a solid ⁇ polymer and had a phase difference of il.
  • the 30-lens polymer was composed of irregularly intertwined fibrils having a diameter of 300 to 400 A.
  • the gel scissors to click ⁇ plated was FUERO plate, room temperature, 1 0 0 K? Bruno ⁇ pressure of a flexible bracelet molded at a metallic luster reddish brown acetylene high polymer with a film of is ⁇ 7to the Fi Lum electrical conductivity (direct current four-terminal method) 2 0 C in 6 5 X 1 0- 7 ⁇ , -. 1 ' was cm one first P-type semiconductor.
  • the centrifuge is cooled with liquid oxygen and the gas in the system is evacuated using a vacuum pump.Tto Next, the temperature of the reactor is increased to room temperature, and the catalyst solution is removed with a magnetic stirrer. While stirring, acetylene gas of 1 atm pressure was blown. 1 0 minutes the whole system after from the start of the polymerization reaction was continued Polymerization while maintaining a 1 atm pressure of agar-like gel in summer 2 4 between acetylene gas continued stirring. The whole system was black-brown agar-like. After the polymerization reaction,
  • Example 1 5 The obtained gel is in the form of a gel, which is the same as that of “ ⁇ ” 13]. When molded in the same manner as in Example 13, a flexible film was obtained.
  • Example 1 5 When molded in the same manner as in Example 13, a flexible film was obtained.
  • Example 13 trisacetinolease toner totitanium 5.0 mi and triethylamine Using 27.0 millimoles and using tetrahydrofuran instead of n-heptane, the procedure of Example 1 was repeated except that the catalyst was adjusted and polymerization of acetylene was carried out in the same manner as in Example 13. 3 and ⁇ A gel was obtained.
  • Tris-acetyl cetonato iron 5.0 mmol and triisobutyl luminium 25.0 mmol were used.
  • a catalyst was prepared and polymerization of acetylene was carried out in exactly the same manner as in Example 13 except for the above, to obtain Example 13 and a gel.
  • Example 2 In place of the contact titanium and triisobutyl luminium used in Example 1, the tris-cetyl-settler medium was added. Use 0.5 mmol and triisobutyl mini-2.5 mol and use instead of Jettlether. A catalyst was prepared and acetylene was polymerized in the same manner as in Example 14 except that hexane was used.
  • heptane 200 was used as a polymerization solution according to a conventional method, and tetrabutoxytitanium was used as a catalyst.
  • 0.1 mmol of ethynoleum aluminum was charged in the chamber to prepare a catalyst solution.
  • the catalyst solution was a homogeneous 10 solution.
  • the reactor was cooled with liquid oxygen and the gas in the system was evacuated with a vacuum pump.
  • the reactor was cooled to -78 C, the catalyst solution was stirred with a magnetic stirrer, and acetylene gas at a pressure of 1 atm was blown.
  • acetylene gas at a pressure of 1 atm was blown.
  • black-brown acetylene high polymerization started to precipitate in powder form.
  • the polymerization reaction was carried out for 24 hours with stirring at 178 C while maintaining the pressure of the acetylene gas at 1 atm, but the resulting acetylene high polymer was in powder form.
  • This powdery acetylene high polymer is washed four times with purified w-heptane 200 four times and then vacuumed! Then, a powdery acetylene high polymer was obtained.
  • This powdery acetylene high polymer has a humidified appearance. Pressed in a room at 100 1 in a room ⁇
  • the product was extremely thin and could not be obtained in the form of a film.
  • 1-n-heptane 20 Q ⁇ was purified as a polymerization solution according to a conventional method, and tetrahydroxititanium was used as a catalyst.
  • the catalyst solution was prepared by charging lyethylaluminum 80 milliliters.
  • the catalyst solution was a homogeneous solution.o
  • acetylene was polymerized in the same manner as in Example 13 using the obtained catalyst solution, the acetylene high polymer " ⁇ 3 ⁇ 4 was in a gel state, acetylene high polymer majority had @ phase partial ⁇ 3 ⁇ 4 a high polymer solid mass 0
  • Example 13 After the post-treatment was carried out satisfactorily as in Example 13, and then the sword was formed in the same manner as in Example 13, a uniform film could not be obtained.
  • Toluene 20 Q ⁇ £ which was purified by a conventional method, was used as the polymerization solvent in the 1 glass reactor completely exchanged with the nitrogen gas, and 2.94 milimol of tetrabutoxytitanium and triethyl were used as the catalyst. 7.34 mmol of aluminum was sequentially charged at room temperature to prepare a catalyst solution. The catalyst solution was a homogeneous solution. The reactor was cooled with liquid nitrogen and the room gas in the system was evacuated with a vacuum pump.
  • the solution was repeatedly washed four times with toluene, and after the washing, the solution was slightly brown and the touch was completely removed.
  • the gel-like acetylene polymer swollen in toluene is one in which fibrils are entangled improperly]), and a powdery, rose-like polymer was generated.
  • a porous acetylene high polymer was obtained and observed with a scanning electron microscope. As a result, the polymer had a fibril structure with a diameter of 200 to 300 A.
  • This porous acetylene high polymer has a cis content of 94% and an electric conductivity of 4.7 XI 0 — 9 ⁇ — —-cm — 1 ? ) Type ⁇ body.
  • This porous acetylene high polymer is usually press-molded at a pressure of 100 ° to obtain a tough film-like acetylene high polymer having a bulk density of 0.80 ° C.
  • Electrical conductivity is 1.2 X 10 — 8 ⁇ — 1 - ⁇ ⁇ ⁇ : p-type semiconductor.
  • Example 1 8 toluene gel in completion acetylene high polymer was de benzene ⁇ a Shirui, it chamber ⁇ Deyutsuku and dried in vacuo, bulk density of 0.5 4 ⁇ Bruno Hiroshi
  • the acetylene high polymer obtained was a film-like acetylene high polymer which was tough and had no formability. .
  • the reactor was cooled down with a target element, and the room gas in the system was evacuated with a vacuum bomb.
  • the temperature of the reactor was lowered to room temperature, and while stirring the catalyst solution with a magnetic stirrer, acetylene gas at a pressure of 1 atm was injected.
  • acetylene gas at a pressure of 1 atm was injected.
  • This gel is freeze-dried at room temperature and the shape and dimensions of the gel
  • the obtained porous acetylene high polymer was obtained.
  • the obtained highly-co-porous polystyrene copolymer has the same fibril structure as that obtained in Example 18, has a bulk density of 0.0 ⁇ no cd, and a cis-a content of 60 «3 ⁇ 4, ' 3 ⁇ 4Air conduction ⁇ is 5.7 X 10 " 8
  • the polymerization reaction was continued for 24 hours while maintaining the acetylene gas pressure 3 ⁇ 41.
  • the system was red-purple agar-like.
  • unreacted acetylene gas was removed, and the system was washed four times with 200 parts of toluene while maintaining the system temperature at 178C. After washing, the solution was still brown and the catalyst was not completely removed.
  • the gel-like styrene polymer swollen in toluene is a uniform 3 ⁇ 4 gel-like substance in which fibrils with a diameter of 200 to 500 A are intertwined irregularly!
  • a powdery or polymer is formed, and a uniform gel-like " ⁇ " is extracted and dried to form a gel ⁇ /
  • the acetylene high polymer was contained in 10% by weight in the gel.
  • the film-shaped product was put in a flask, and air was evacuated with a pump. Then, iodine gas was introduced at room temperature vapor pressure of iodine, and the film-shaped molded product was formed for 1 hour. 1 I noticed unsulfur iodine with a pump and iodine; This film-shaped molded product had a gas conductivity of 20 mm and was 95 ⁇ - 1 cm ⁇ ⁇ D-type semiconductor.
  • Example 21 The homogenous gel obtained by polymerization in Example 21 (containing 10% by weight of acetylene high polymer) was vacuum-dried to obtain a gel of 50 heavy acetylene high polymer.
  • This product has an electrical conductivity of 20 and 4.1 X 10 _ S a _ 1 ⁇ cm- 1 ? It was a type semiconductor.
  • arsenic pentafluoride® molded product had an electric conductivity of 20 C and was' cm ⁇ : P-type semiconductor.
  • Example 21 Replacement of toluene used as polymerization solvent in 1! The catalyst was prepared and acetylene was weighed in the same manner as in Example 21 except that Rysol was used in (2) to obtain a uniform gel. ⁇ 4 of the acetylene high polymer in the gel extraction was 12 doubles. ⁇
  • Example 21 The preparation of the catalyst and the polymerization of acetylene were carried out in the same manner as in Example 21 except that the polymerization of acetylene was carried out at room temperature in Example 21 to obtain a uniform gel.
  • the high acetylene polymer content in this gel is 18 wt. 7 o (Press molding method for gel autumn)
  • Acetylene having a fipril structure produced by the method of the present invention
  • the porous acetylene highly polymerized book obtained by drying is obtained by the pressure molding method of the present invention. It is very useful because it can make any meat and make any shape with high mechanical strength.
  • the molded article of the acetylene high polymer obtained in this way has a very low resistance and exhibits various semiconductor-specific aerodynamic properties.
  • acetylene high polymer utilizes the above-mentioned various electrical properties], for example, an electric resistance element, a heat-sensitive element, a photosensitive element, or an organic semiconductor material for manufacturing electric machine parts. Can be used as
  • electron-accepting compounds ⁇ include iodine, bromine, bromine iodide, pentafluorine, pentafluoride antimony, silicon tetrafluoride, phosphorus pentachloride, phosphorus pentafluoride, and phosphorus salt Lumi, Odoriya Noremi, Pakishi Xisulfuryl Difluoride Sulfur, Nitrogen, Full Sulfur ⁇ , Trifluoromethansulfone, Chromium Sulfur ⁇ , Boron Trichloride, Boron Tribromide, Three He can be cited as ⁇ , ⁇ , or ⁇ .
  • the conductive acetylene high polymer obtained in this manner exhibits high air conductivity depending on the type of electron-accepting compound and the type of the child. -9 ⁇ :! .
  • P-type or w-type semiconductor that can be freely controlled in the range of 3 ⁇ — 1 -an ⁇ ⁇ ?, As it is Flexible and useful as an electronic device It can be used as a conductive material It is not possible to use a D-type semiconductor, and it can be easily combined with a w-type or p-type semiconductor to form a heterojunction device.
  • the band gap energy of acetylene high polymer is 1.6 e to 1.9 e and photoconductivity with visible light.] 5
  • As a material for heavy 'electrical transducers such as solar cells and optical sensors Is also useful.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electromagnetism (AREA)
  • Health & Medical Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
PCT/JP1980/000053 1979-03-29 1980-03-28 Process for preparing gel-like composition of acetylene high polymer,and process for fabrication thereof WO1980002143A1 (en)

Priority Applications (1)

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DE19803041421 DE3041421C2 (de) 1979-03-29 1980-03-28 Verfahren zur Herstellung sowohl einer leicht formbaren Masse aus einem Acetylenhochpolymeren als auch eines por¦sen Acetylenhochpolymeren

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JP3628879A JPS55128419A (en) 1979-03-29 1979-03-29 Forming method for acetylene high polymer
JP3628379A JPS55129404A (en) 1979-03-29 1979-03-29 Preparation of homogeneous gel of acetylene high polymer
JP79/36288 1979-03-29
JP5024479A JPS6028300B2 (ja) 1979-04-25 1979-04-25 フイブリル構造を有する多孔質アセチレン高重合体の製造方法
JP5401779A JPS55145710A (en) 1979-05-04 1979-05-04 Preparation of gellike material of high-molecular acetylene polymer
JP5401879A JPS55145711A (en) 1979-05-04 1979-05-04 Preparation of gellike material of high-molecular acetylene polymer

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0049970A1 (en) * 1980-10-06 1982-04-21 Rohm And Haas Company High drain battery
EP0058469B1 (en) * 1981-01-22 1987-07-22 Showa Denko Kabushiki Kaisha Battery having acetylene high polymer electrode

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2061291B (en) * 1979-03-29 1983-04-20 Showa Denko Kk Process for preparing highly conductive acetylene high polymer
EP0076119B1 (en) * 1981-09-25 1986-07-23 Showa Denko Kabushiki Kaisha Reinforced acetylene high polymers, process for preparing same and battery having same
DE3147476A1 (de) * 1981-12-01 1983-07-14 Bayer Ag, 5090 Leverkusen Dotierte polymere organische leiter und verfahren zu ihrer herstellung
US4394304A (en) * 1982-01-29 1983-07-19 Massachusetts Institute Of Technology Electrically conducting polymer blends
US4600756A (en) * 1982-08-03 1986-07-15 Enichimica S.P.A. High-orientability polyacetylene films and process for their production
DE3421993C1 (de) * 1984-06-14 1985-12-12 Zipperling Kessler & Co (Gmbh & Co), 2070 Ahrensburg Verfahren zur Herstellung von Formteilen aus elektrisch leitfaehigen organischen Polymeren und/oder organischen Leitern,Vorrichtung zur Durchfuehrung des Verfahrens sowie Verwendung der Formteile
US4866147A (en) * 1985-07-30 1989-09-12 The United States Of America As Represented By The United States Department Of Energy Soluble silylated polyacetylene derivatives and their use as percursors to novel polyacetylene-type polymers
DE3617505A1 (de) * 1986-05-24 1987-11-26 Basf Ag Hochleitfaehiges filmfoermiges polyacethylen
US5216102A (en) * 1988-08-05 1993-06-01 Matsushita Electric Industrial Co., Ltd. Process for producing polyacetylene
US5716708A (en) * 1995-01-17 1998-02-10 Lagow; Richard J. Acetylenic carbon allotrope
JP3162313B2 (ja) * 1997-01-20 2001-04-25 工業技術院長 薄膜製造方法および薄膜製造装置
ES2165280B1 (es) * 1999-07-21 2003-05-01 Univ Valencia Politecnica Un material util como conductor electrico que comprende poliacetileno o poliacetilenos sustituidos incorporados en un soporte mesoporoso, procedimiento para obtener el material y conductores que comprenden el material.
ATE356443T1 (de) * 2005-04-21 2007-03-15 Inpro Innovations Gmbh Verfahren zur herstellung polymerer elektrisch leitender schichten

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BE548927A (bs) * 1955-03-18
BE558728A (bs) * 1956-06-27
GB1294406A (en) * 1969-05-05 1972-10-25 Polymer Corp Porous compositions and process for making thereof
JPS4832581A (bs) * 1971-08-31 1973-04-28
US3933722A (en) * 1973-04-20 1976-01-20 General Electric Company Meet extrudable polyacetylene copolymer blends
US4228060A (en) * 1978-11-03 1980-10-14 Allied Chemical Corporation Polymerization of acetylene
US4362680A (en) * 1980-03-21 1982-12-07 Showa Denko K.K. Process for production of molded articles of acetylene polymer

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0049970A1 (en) * 1980-10-06 1982-04-21 Rohm And Haas Company High drain battery
EP0058469B1 (en) * 1981-01-22 1987-07-22 Showa Denko Kabushiki Kaisha Battery having acetylene high polymer electrode

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DE3041421T1 (bs) 1981-04-23
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EP0026235A1 (en) 1981-04-08
EP0026235B1 (en) 1986-12-10
GB2058096B (en) 1983-04-20
GB2058096A (en) 1981-04-08
US4596852A (en) 1986-06-24
EP0026235A4 (fr) 1981-10-13

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